EP0669330A1 - Dimère de beonzotriazole utiles comme absorbant UV - Google Patents

Dimère de beonzotriazole utiles comme absorbant UV Download PDF

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Publication number
EP0669330A1
EP0669330A1 EP95810099A EP95810099A EP0669330A1 EP 0669330 A1 EP0669330 A1 EP 0669330A1 EP 95810099 A EP95810099 A EP 95810099A EP 95810099 A EP95810099 A EP 95810099A EP 0669330 A1 EP0669330 A1 EP 0669330A1
Authority
EP
European Patent Office
Prior art keywords
tert
butyl
bis
oder
hydroxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95810099A
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German (de)
English (en)
Other versions
EP0669330B1 (fr
Inventor
Dieter Dr. Reinehr
Jean-Pierre Bacher
André Dr. Schmitter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Geigy AG
Ciba Spezialitaetenchemie Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG, Ciba Spezialitaetenchemie Holding AG filed Critical Ciba Geigy AG
Publication of EP0669330A1 publication Critical patent/EP0669330A1/fr
Application granted granted Critical
Publication of EP0669330B1 publication Critical patent/EP0669330B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings

Definitions

  • the invention relates to new dimeric 2- (2'-hydroxyphenyl) benzotriazoles, their use as stabilizers for organic polymers, corresponding stabilized compositions and a process for stabilizing organic polymers.
  • Certain 2- (2'-hydroxyphenyl) benzotriazoles have long been used as stabilizers for organic polymers. The use of some dimeric compounds of this type is also described. For example, some methylene-bridged bis-benzotriazoles are known from US-A-4,812,498, US-A-4,948,666 and US-A-4,681,905; US-A-4 859 726 describes 2- (2'-hydroxyphenyl) benzotriazoles which are chemically bonded to one another in the 3 'position via di-isopropylidene benzene.
  • DE-A-2 536 335, GB-A-1 169 859 and CH-A-408 033 describe some 2- (2'-hydroxyphenyl) benzotriazoles which bear a -CH2-N type in the 3 'position (R) -CO-R, where R stands for certain organic radicals and which can also be used as light stabilizers.
  • the invention relates to new dimeric benzotriazoles which are surprisingly suitable for stabilizing organic polymers against the damaging influence of heat, oxygen and light, in particular UV radiation.
  • the invention therefore relates to compounds of the formula I. wherein p is 0 or 1;
  • A represents C1-C12 alkylene;
  • R1 and R'1 independently of one another are hydrogen, halogen, C1-C18-alkyl, C1-C18-alkoxy or -CN;
  • R2 and R'2 independently represent hydrogen or C1-C18 alkyl or together represent C2-C12 alkylene or C2-C12 hydroxyalkylene; and
  • R3 and R'3 are independently hydrogen, halogen, C1-C18 alkyl or C1-C18 alkoxy.
  • R1 and R'1 independently represent hydrogen, halogen, C1-C12-alkyl, C1-C12-alkoxy or -CN; R2 and R'2 independently represent hydrogen or C1-C12-alkyl or together C2-C3-alkylene or C2-C3-hydroxyalkylene; and R3 and R'3 independently of one another are hydrogen, chlorine, C1-C12-alkyl or C1-C12-alkoxy.
  • Halogen means -F, -Cl, -Br or -I; in all embodiments of the invention a halogen substituent is preferably -Cl or -Br; especially -Cl.
  • alkylene means methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene or dodecylene. Is preferred C1-C8 alkylene, especially straight-chain C1-C8 alkylene.
  • R1, R'1, R2, R'2, R3 and R'3 are, independently of one another, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, independently of one another , Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl; C1-C12-alkyl is preferred, especially C1-C9-alkyl.
  • R1, R'1, R2 and R'2 represent as alkyl, independently of one another, preferably C1-C,-alkyl, especially methyl.
  • R3 and R'3 as alkyl are preferably, independently of one another, either methyl or branched-chain C4-C12-alkyl, in particular methyl or tertiary C4-C8-alkyl.
  • a tertiary alkyl group denotes a saturated aliphatic hydrocarbon radical, the binding carbon atom of which in turn binds to 3 further carbon atoms.
  • Examples of tertiary C4-C8-alkyl include tert-butyl (1,1-dimethylethyl) or tert-octyl (1,1,3,3-tetramethylbutyl).
  • R1 and R'1 as well as R3 and R'3 each represent the same radicals.
  • R2 and R'2 are, unless they together represent alkylene or hydroxyalkylene, identical radicals.
  • R2 and R'2 together represent alkylene or hydroxyalkylene, then p is generally 0; R2 and R'2 then preferably form together with the urea unit to which they are attached, a five-membered or six-membered ring, especially a 5-membered ring.
  • the ring can be substituted by alkyl or, when R2 and R'2 together have the meaning hydroxyalkylene, additionally by 1 or more -OH.
  • R2 and R'2 are particularly preferably alkylene or hydroxyalkylene together 1,2-ethylene, 1,3-propylene, 1,2-ethylene substituted by 1 or 2 -OH or 1,3-propylene substituted by 1 or 2-OH , especially 1,2-ethylene or 1,2-ethylene substituted by 1 or 2-OH.
  • the compounds according to the invention can be prepared analogously to one of the processes described in DE-A-2 536 335, GB-A-1 169 859 or CH-A-408 033.
  • one equivalent of a benzotriazole of the formula II and an equivalent of a benzotriazole of the formula II ' with one equivalent of a compound of formula III implemented.
  • A, R1, R'1, R2, R'2, R3, R'3 and p have the meanings given above for formula I;
  • X stands for OH, halogen or alkoxy.
  • the temperature of the reaction is not critical and can be, for example, -10 ° C to + 150 ° C;
  • the reaction advantageously takes place in a suitable reaction medium (for example in an acid or in an organic solvent) in the presence of a suitable additive (for example an acid, an alkali compound, a dehydrating agent), where the reaction medium and additive can be identical.
  • a compound of the formula I for example, compounds of the formulas II and II ', which are identical or different, with the compound of the formula III in concentrated sulfuric acid, for example with 80-100% H2SO4, in a mixture of acetic anhydride and glacial acetic acid , in polyphosphoric acid (approx. 100 to 130% phosphorus based on orthophosphoric acid), or in an inert solvent such as toluene or hexane with the addition of a dehydrating agent such as p-toluenesulfonic acid or aluminum chloride, advantageously with stirring.
  • concentrated sulfuric acid for example with 80-100% H2SO4
  • polyphosphoric acid approximately 100 to 130% phosphorus based on orthophosphoric acid
  • a dehydrating agent such as p-toluenesulfonic acid or aluminum chloride
  • Sulfuric acid is preferably used and the reaction is carried out at -5 ° C to + 40 ° C, the temperature of the reaction mixture after metering in all components preferably in the range from 0 ° C to 30 ° C, especially 15 ° C to 25 ° C (room temperature ) is held.
  • the product can be worked up and isolated in a known manner, for example by dilution with water, advantageously with cooling (ice water), filtering off the solid product and then washing and drying.
  • the compounds of the formula I according to the invention can be used particularly advantageously in compositions which contain an organic polymer, for example a synthetic organic polymer, as component A.
  • the compounds of the formula I are of particular importance for stabilizing compositions which contain a thermoplastic polymer.
  • compositions according to the invention can be part of a coating composition, for example a lacquer, or a plastic composition.
  • Thermoplastic polymers containing heteroatoms in the main chain are primarily O, S and N containing polymers. Examples of this can be found in points 13 to 20 of the list above. Preferred are among them the polycarbonates, polyesters, polyamides, polyacetals, polyphenylene oxides and polyphenylene sulfides; in particular polycarbonates, polyesters such as polyethylene terephthalate (PET), and polyamides (PA) such as PA 6 or PA 6/6; but above all the polycarbonates.
  • PET polyethylene terephthalate
  • PA polyamides
  • lacquers can be applied as single-layer or two-layer lacquers, the stabilizers according to the invention preferably being added to the unpigmented top layer.
  • the lacquers can be applied to the substrates (metal, plastic, wood, etc.) by the usual methods, for example by brushing, spraying, pouring, dipping or electrophoresis.
  • a preferred embodiment of the present invention is therefore paints or varnishes (e.g. automotive paints) which contain at least one compound according to the invention.
  • suitable binders are those mentioned above.
  • the invention also relates to a process for stabilizing organic material, in particular organic polymers, against damage by light, oxygen and / or heat, characterized in that a compound of the formula I is added to this as a stabilizer, and the use of compounds of the formula I to stabilize organic material.
  • the amount of stabilizer to be used depends on the organic material to be stabilized and the intended use of the stabilized material.
  • the composition according to the invention contains 0.01 to 15, especially 0.1 to 5 parts by weight of the stabilizer (component B) per 100 parts by weight of component A.
  • incorporation into the organic polymers can take place, for example, by mixing in the compounds according to the invention and, if appropriate, further additives by the methods customary in industry.
  • the incorporation can be carried out before or during shaping, for example by mixing the powdery components or by adding the stabilizer to the melt or solution of the polymer, or by application of the dissolved or dispersed compounds on the polymer, optionally with subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as latices.
  • Another way of incorporating the compounds according to the invention into polymers is to add them before or during the polymerization of the corresponding monomers or before crosslinking.
  • the compounds according to the invention or mixtures thereof can also be added to the plastics to be stabilized in the form of a masterbatch which contains these compounds, for example in a concentration of 2.5 to 25% by weight.
  • the stabilized polymer compositions thus obtained can be prepared by the usual methods, e.g. by hot pressing, spinning, extruding or injection molding, into molded articles, e.g. in fibers, foils, tapes, plates, multi-wall sheets, vessels, pipes and other profiles.
  • the invention therefore further relates to the use of the polymer composition according to the invention for the production of a shaped article.
  • a polymer composition according to the invention with a relatively high content of stabilizer of the formula Ib, for example 5-15% by weight, is applied in a thin layer (10-100 ⁇ m) to a molded article made of a polymer which has little or no stabilizer of the formula Ib contains, applied.
  • the application can take place simultaneously with the shaping of the base body, for example by so-called coextrusion. However, it can also be applied to the fully formed base body, for example by lamination with a film or by coating with a solution.
  • the outer layer or the outer layers of the finished object have the function of a UV filter, which Protects the inside of the object against UV light.
  • the outer layer preferably contains 5-15% by weight, in particular 5-10% by weight, of at least one stabilizer of the formula Ib.
  • the outer layer (s) consisting of a polymer composition according to the invention in a thickness of 10-100 ⁇ m, while the inner layer contains little or no stabilizer of the formula Ib, therefore constitutes one further object of the invention.
  • the polymers stabilized in this way are characterized by high weather resistance, especially by high resistance to UV light. As a result, they retain their mechanical properties as well as their color and gloss for a long time, even when used outdoors.
  • the type and amount of further stabilizers added is determined by the type of substrate to be stabilized and its intended use; 0.1 to 5% by weight, based on the polymer to be stabilized, is frequently used.
  • the mixture is then stirred for a further 2 hours at + 20 ° C, poured onto 11 ice water, filtered off and washed neutral with water.
  • the filter cake is stirred with 600 ml of dimethylacetamide, heated to 100 ° C., cooled and then filtered off. After washing with dimethylacetamide and water and then drying at 100 ° C. in a vacuum drying cabinet, 42 g of a white powder with a melting point of 283.5 ° C. are obtained, corresponding to a yield of 74.9%.
  • the films are pulled off the glass plates and stretched in cardboard frames (6 x 3 cm). These samples are irradiated for 3 months in a UV exposure device with 5 fluorescent lamps TL / 09 and 5 lamps TL / 12, which are mounted 20 cm above the samples. The UV absorption is measured at regular intervals at the wavelength of maximum extinction. The discoloration of the samples is also checked by measuring the yellowness index (YI, method ASTM D 1925).
  • the samples stabilized according to the invention have excellent light resistance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
EP95810099A 1994-02-24 1995-02-15 Dimères de benzotriazole utiles comme absorbant UV Expired - Lifetime EP0669330B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH55494 1994-02-24
CH554/94 1994-02-24

Publications (2)

Publication Number Publication Date
EP0669330A1 true EP0669330A1 (fr) 1995-08-30
EP0669330B1 EP0669330B1 (fr) 1998-08-05

Family

ID=4189686

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95810099A Expired - Lifetime EP0669330B1 (fr) 1994-02-24 1995-02-15 Dimères de benzotriazole utiles comme absorbant UV

Country Status (7)

Country Link
US (2) US5488112A (fr)
EP (1) EP0669330B1 (fr)
JP (1) JPH07258228A (fr)
KR (1) KR950032148A (fr)
CA (1) CA2143165A1 (fr)
DE (1) DE59503032D1 (fr)
TW (1) TW332827B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999037638A1 (fr) * 1998-01-27 1999-07-29 Great Lakes Chemical (Europe) Gmbh 2-(2'-hydroxyphenil) benzotriazoles contenant un groupe 2,4-imidazolidinedione et procede de preparation de ces composes
WO2001036396A1 (fr) * 1999-11-16 2001-05-25 Ciba Specialty Chemicals Holding Inc. Utilisation d'absorbeurs uv a base de benzotriazole
WO2014026780A1 (fr) 2012-08-16 2014-02-20 Basf Coatings Gmbh Compositions de revêtement comprenant des absorbeurs d'uv à base de benzotriazole

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69810527T2 (de) * 1997-03-27 2004-11-04 Great Lakes Chemical (Europe) Gmbh 2-(2'-Hydroxphenyl)-benzotriazole und ihre Verwendung als Lichtschutzmittel für organische Polymere
BR9911024A (pt) 1998-05-19 2001-02-06 E I Pont De Nemours And Compan Composição de revestimento e método de produção de um revestimento em um substrato.
US6245915B1 (en) 1999-05-03 2001-06-12 Ciba Specialty Chemicals Corporation Asymmetrical bisbenzotriazoles substituted by a perfluoroalkyl moiety
US6251173B1 (en) 1999-10-29 2001-06-26 Lexmark International, Inc. Ink compositions containing ultraviolet absorbers
US6284895B1 (en) * 2000-12-27 2001-09-04 Council Of Scientific And Industrial Research Bromo-functionalized benzotriazole UV absorbers
US8129309B2 (en) 2007-03-29 2012-03-06 Fujifilm Corporation Heat-sensitive transfer sheet for use in heat-sensitive transfer system and image-forming method using heat-sensitive transfer system
EP1974948A3 (fr) 2007-03-29 2012-02-08 FUJIFILM Corporation Procédé de formation d'images utilisant un système de transfert thermosensible
US8119562B2 (en) 2007-03-29 2012-02-21 Fujifilm Corporation Heat-sensitive transfer sheet and image-forming method using heat-sensitive transfer system
JP2008273641A (ja) 2007-04-25 2008-11-13 Fujifilm Corp 感熱転写受像シート用紙管、感熱転写受像シートのロール形態加工物、及び画像形成方法
JP5544239B2 (ja) 2010-07-29 2014-07-09 富士フイルム株式会社 重合性組成物
CN109517172B (zh) * 2017-09-18 2023-08-29 嘉兴山蒲照明电器有限公司 一种有机硅改性聚酰亚胺树脂组合物及其应用

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH408033A (de) * 1961-06-16 1966-02-28 Geigy Ag J R Verfahren zur Herstellung von substituierten 2-(2'-Hydroxyphenyl)-benztriazolverbindungen
CH410851A (de) * 1961-06-16 1966-10-31 Geigy Ag J R Verfahren zum Schützen von Textilmaterial gegen Lichtschädigung
US3399173A (en) * 1961-06-16 1968-08-27 Geigy Ag J R Light-stable polyaddition compounds
CH497919A (de) * 1961-06-16 1970-10-31 Geigy Ag J R Verwendung von substituierten 2-(2'-Hydroxyphenyl)-benztriazolverbindungen als Lichtschutzmittel
DE2536335A1 (de) * 1974-08-15 1976-02-26 Kyodo Chemical Co Ltd 1,2,3-triazolverbindungen, verfahren zu ihrer herstellung und ihre verwendung als ultraviolettabsorber
US4681905A (en) * 1984-11-07 1987-07-21 Adeka Argus Chemical Co., Ltd. Stabilizer compositions for synthetic resins imparting improved light stability
US4812498A (en) * 1986-12-22 1989-03-14 Adeka Argus Chemical Co., Ltd. Polycarbonate resin compositions having improved resistance to deterioration when exposed to light and containing alkylidene bis(benzotriazolyl phenols)
US4859726A (en) * 1988-10-24 1989-08-22 Eastman Kodak Company Bis-benzotriazolyl compounds and polymeric materials stabilized therewith
US4948666A (en) * 1988-04-22 1990-08-14 Mobay Corporation Stain resistant polycarbonate panels
US5233047A (en) * 1987-08-12 1993-08-03 Elf Atochem North America, Inc. Benzotriazole UV absorber hydrazides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6809017A (fr) * 1967-07-01 1969-01-03

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH408033A (de) * 1961-06-16 1966-02-28 Geigy Ag J R Verfahren zur Herstellung von substituierten 2-(2'-Hydroxyphenyl)-benztriazolverbindungen
CH410851A (de) * 1961-06-16 1966-10-31 Geigy Ag J R Verfahren zum Schützen von Textilmaterial gegen Lichtschädigung
US3399173A (en) * 1961-06-16 1968-08-27 Geigy Ag J R Light-stable polyaddition compounds
CH497919A (de) * 1961-06-16 1970-10-31 Geigy Ag J R Verwendung von substituierten 2-(2'-Hydroxyphenyl)-benztriazolverbindungen als Lichtschutzmittel
DE2536335A1 (de) * 1974-08-15 1976-02-26 Kyodo Chemical Co Ltd 1,2,3-triazolverbindungen, verfahren zu ihrer herstellung und ihre verwendung als ultraviolettabsorber
US4681905A (en) * 1984-11-07 1987-07-21 Adeka Argus Chemical Co., Ltd. Stabilizer compositions for synthetic resins imparting improved light stability
US4812498A (en) * 1986-12-22 1989-03-14 Adeka Argus Chemical Co., Ltd. Polycarbonate resin compositions having improved resistance to deterioration when exposed to light and containing alkylidene bis(benzotriazolyl phenols)
US4812498B1 (en) * 1986-12-22 1995-04-11 Adeka Argus Chemical Co Ltd Polycarbonate resin compositions having improved resistance to deterioration when exposed to light and containing alkylidene bis(benzotriazolyl phenols).
US5233047A (en) * 1987-08-12 1993-08-03 Elf Atochem North America, Inc. Benzotriazole UV absorber hydrazides
US4948666A (en) * 1988-04-22 1990-08-14 Mobay Corporation Stain resistant polycarbonate panels
US4859726A (en) * 1988-10-24 1989-08-22 Eastman Kodak Company Bis-benzotriazolyl compounds and polymeric materials stabilized therewith

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999037638A1 (fr) * 1998-01-27 1999-07-29 Great Lakes Chemical (Europe) Gmbh 2-(2'-hydroxyphenil) benzotriazoles contenant un groupe 2,4-imidazolidinedione et procede de preparation de ces composes
US6452018B1 (en) 1998-01-27 2002-09-17 Great Lakes Chemical Italia S. R. L. 2-(2′-hydroxyphenyl) benzotriazoles containing a 2,4-imidazolidinedione group and process for their preparation
WO2001036396A1 (fr) * 1999-11-16 2001-05-25 Ciba Specialty Chemicals Holding Inc. Utilisation d'absorbeurs uv a base de benzotriazole
US7066184B1 (en) 1999-11-16 2006-06-27 Ciba Specialty Chemicals Corporation Use of benzotriazole UV absorbers
US7129198B1 (en) 1999-11-16 2006-10-31 Ciba Specialty Chemicals Corporation Use of benzotriazole UV absorbers
US7179924B2 (en) 1999-11-16 2007-02-20 Ciba Specialty Chemicals Corporation Use of benzotriazole UV absorbers
WO2014026780A1 (fr) 2012-08-16 2014-02-20 Basf Coatings Gmbh Compositions de revêtement comprenant des absorbeurs d'uv à base de benzotriazole

Also Published As

Publication number Publication date
JPH07258228A (ja) 1995-10-09
DE59503032D1 (de) 1998-09-10
TW332827B (en) 1998-06-01
EP0669330B1 (fr) 1998-08-05
CA2143165A1 (fr) 1995-08-25
US5589529A (en) 1996-12-31
US5488112A (en) 1996-01-30
KR950032148A (ko) 1995-12-20

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